Stabilized ice color composition containing guanylurea



Patented Mar. 23, 1943 STABILIZED ICE COLOR COIWPOSITION CONTAINING GUANYLUREA Paul P. McClellan, Old Greenwich, and ,Walter P. Ericks, Cos Cob, Conn, assignors to American Cyanamid Compan New York, N. Y., a corporation of Maine No Drawing. Application August so, 1941, Serial No. 409,063

6 Claims: (01.- 8-45) This invention relates to a new class of chemical compounds, to intermediates and dyes obtained therefrom, and to their methods of preparation.

The principal object of this invention is to prepare new stabilized diazo compounds, preferably those soluble in Water and in the more commonly used organic solvents.

Among the stabilized diazo compounds included herein are, more especially, the reaction products of an ice color diazo component with an alkylol or an alkoxyalkylol derivative of guanylurea. Inasmuch as these derivatives each exist in several tautomeric forms, the reaction products prepared from any one may occur as a mixture of isomers which readily undergo rearrangement. Hence, assignment of a definite chemical formula is problematical.

However, the chemical properties of the products and the particular method or methods of preparation disclosed herein cause one of the isomers to appear in excess, and under the present conditions the monomeric form is produced predominantly. Thus the alkylol and alkoxyalkylol guanylurea derivatives probably give:

r r H R-N=N1\I o-NHo-1-'IR2 NH c in which R represents the nucleus of an aro matic amine such as the nucleus of an ice color diazo component; and R2 is an alkylol or alkoxyalkylol group,

' These stabilized diazocompounds are resistant to percussion and even when heated in a direct flame decompose without the hazard of an explosion. When in a dry condition or in an alkaline solution they are stable at temperatures normally encountered throughout all seasons of the year, and hence may be stored indefinitely. However, these reaction products possess the property of splitting into their original components by treatment with acids at elevated temperatures or with steam containing volatile acid vapors. If this splitting occurs in the presence of an ice color coupling component the regenerated active diazotized component becomes available immediately for reaction with thecoupling component and produces the corresponding azo pigment or dye. I

To this end it is a further objectof this invention to prepare new azo pigments and dyes by mixing an ice color coupling component and the reaction product of an ice color diazo component with an alkylol or alkoxyalkylol derivative of guanylurea.

it into its components; and the regenerated di- I As such, the mixture may or may not be colored. However, if a textile material is printed or impregnated with this mixture and nent (e. g. naphthol in the example given below) tile acid vapors.

azotized component liberated couples with the ice color coupling component to form an azo pi ment or dye.

This acid treatment or ageingas it is called,

is preferably effected with a weak acid and at Usually formic or. acetic acids are used, but various other acids as an elevated temperature.

well as substances liberating acids upon being steamed such as ammonium sulfate, esters of tartaric, succinic, etc., acids may be used particularly when the printed material is subjected to a subsequent steam treatment to effect ageing or develop the color.

Stable alkaline printing pastes can be prepared from the mixture of the ice color coupling component and the reaction product of the ice color diazo component with one of the alkylol or alkoxyalkylol derivatives by dissolving the mixture in a solvent such as water, alcohoLacetone, etc., together with various other ingredients such as alka'lies, organic bases, impregnating agents, thickeners such as starch, gum, etc., well known to those skilled in the art. Cotton goods can-be printed with this paste with the aid of a copper roll. The print is then dried and subsequentlythe desired color is developed by steaming in the presence of acetic acid or other vola- In this manner an insoluble azo pigment is produced in and on the cotton fibers in the form of the printed pattern. Such prints based upon the ease with which the stabilized diazamino group present can be split and converted into an active diazo group by heating in the presence of an acid or an acid liberating.

substance. This conversion or ageing is usually effected in a steam chamber and in the presence of a coupling component. Under these condiv tions the active diazo group is free for such a short time interval that it does not decompose and instead couples with the coupling compoto develop or form the color.

The following example describes the preparation of several stabilized diazo compounds in cluded in this invention and further gives details as to their use in dyeing and printing textile materials. EXAMPLE Ethylol guanylurea reacted with p-toluidine diazom'um hydrochloride 7 An aqueous solution of ethylol guanylurea was prepared by reacting 33.8 g. of guanylurea sul- 10 C. with 8.8 g. of ethylene oxide. It was then reacted for anadditional 3 hours while cooled and stirred and then further cooled to C.

23.1 g. of p-toluidine diazonium chloride was added to the above ethylol guanylurea solution with stirring. A brown powder precipitated out and was filtered off and dried at room temperature.

This diazo compound has the following probable formula:

thoic acid, or the 4-chloranilide of 2,3-hydroxynaphthoic acid. When mixed with an alkaline solution of sodium aenaphtholate it was stable but the formation of a red azo dyestuff upon addition of acetic acid and heating the mixture showed that coupling was readily effected in an acid medium at an elevated temperature.

Similarly, various other members of the alkylol and alkoxyalkylol series of derivatives of guanylurea may be obtained by using as a starting material the corresponding compound containing a reactive ethylene oxide ring and a corresponding substituent'in the ethylene oxide ring. Thus instead of ethylene oxide, one or more mol. of glycidol, propylene oxide, isopropylene oxide, butylene oxide, isobutylene oxide, etc., etc., can be used in order to render the stabilized diazo compound water soluble. A number of such compounds are described in the co-pending applications Serial Numbers 289,398 and 289,400 of Walter P. Ericks.

It is to be particularly'noted that although for ease of description the aromatic amine chosen in the example illustrating specific embodiments of the invention was p-toluidine, various other stable diazo compounds can be prepared from practically any ice color diazo component. Thus other typical amines which can be diazotized and reacted with the stabilizing components include a in addition to p-toluidi-ne, among numerous others familiar to those versed in the art, aniline as well as homologues of aniline, namely 2,4-dimethylaniline. Where still other color variations are desired, the halogen derivatives of aniline may be used, such as the monochloroanilines, dichloranilines; anilines substituted by hydrocarbon radicals, such as alkyl, alkoxy radicals, for example methyl, ethyl, etc., methoxy, ethoxy, or the like; or anilines substituted by nitro radicals, acyl derivatives thereof, and the like.

Similarly, although l-naphthol is given as the most frequently used coupling component for the dye mixture incorporating the specific stabilized diazo compounds, various other naphthols, such as naphthol AS, toluidides, pyrazolones, coupling arylides, particularly arylides of 2,3-hydroxynaphthoic acid, other hydroxy or amino-naphthoic acids, carbazole-carboxylic acid, hydroxyanthracene carboxylic acid, anthraquinone carboxylic acid, the anilide of -2,3-hydroxy-naphthoic acid, or the like, may be used as coupling components.

This case is a continuation-in-part of our copending application serial No. 369,806, filed Dec. 12, 1940.

. fined by the score of the appended claims.

We claim:

1. A color producing composition of matter which comprises an ice color coupling component and a stabilized diazo compound having the formula:

n R-N=N--l ICNH-gl \'lta' NH 0 in which R is the nucleus of an ice color diazo component of the benzene series and R2 is selected from the group consisting of an alkylol and an alkoxyalkylol group.

2. A color producing composition of matter which comprises an ice col'or coupling component and a stabilized diazo compound having the formula:

H ll

u NH 0 in which R is the nuclues of an ice color diazo component of the benzene series and X is a saturated aliphatic radical having at least two carbon atoms.

3. A color producing composition of matter which comprises an ice color coupling component and a stabilized diazo compound having the color coupling component and a stabilized diazo compound having the formula [I n RN==N. I$:JNII-fil I-Ru NH 6 in which R is the "nucleus of an ice color diazo component of the benzene series and R2 is selected from the group consisting of an alkylol and an alkoxyalkylol group.

PAUL P. McCLELLAN. I WALTER}. ERICKS. 

